Method of making siliceous refractories



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-I LE' INVENTOR. James (07. Lamaze June 27, 1961 Filed Sept. 11, 1958 J. MCCLURG LAMBIE 2,990,289

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METHOD OF MAKING SILICEOUS REFRACTORIES Filed Sept. 11, 1958 4 Sheets-Sheet 3 FLUX BODY WITH SILICEOUS 6206 500 400 .500 600 700 TEMPEJZAT'UEE DEGBEES C.

N FIRED N OF THE FREE CURVE B SHOWS THE. BODY FIRED TD SUCH A TEMPERATURE AND FOR SUCH A TIME THAT A POBTIO SI LICA HAS RYSTALLI ZED AS CRISTOBALITE- CURVE A SHOWS TIME T 06 E U E a-M T #O C 1 BALITE IS FORMED 2C0 TEMPERATURE, DEGREES C.

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METHOD OF MAKING SILICEOUS REFRACTORIES Filed Sept. 11, 1958 4 Sheets-Sheet 4 m m U Q 6 w u w s A I S w mi G 1 z m. M w 6 m/ w A 4m, 4 u 07 v Qi 9, 0 1!!!! 1- X w HJJHZ OOH ZH 2932533 THERMAL EXPANSION OF SILICA MINERALS INVENTOR. James (6') Lamaze:

Ju's EMEJY United States Patent F 2,990,289 METHOD OF MAKING SILICEOUS REFRACTORIES James McClnrg Lambie, Washington, Pa., assignor to Findlay Refractories Company, Washington, Pa., a corporation of Pennsylvania Filed Sept. 11, 1958, Ser. No. 760,468 3 Claims. (Cl. 106-68) This invention relates to the improvement of refractories especially those used against molten glass. Specifically, the purpose of the process is to make such refractories with minimum porosity (and thus more resistant to solution by molten glass) and higher in silica content. The refractory is therefore closer to the composition of glass, and upon erosion thereof by the molten glass will introduce less contamination into the melt. I

This application concerns the making of a grog that will be a non-porous, glassy material, having a high silica content and a low expansion up to 800 C. The grog is used together with raw bonding clays and fines which we call the matrix, to make a body out of which is made glass melting pots, tank blocks, drawbars, and other refractory pieces.

One object of the invention is to make a dense, highsilica refractory where the silica content of the grog is as high or higher than that of the matrix, as distinguished from grogs of flint clays, which are less siliceous than the bonding clays. The word (dense) is here used in the sense of low porosity.

Another purpose is to make a high silica grog which possesses various advantages that result from near zero porosity.

Another purpose is to make a refractory that will have a low coefiicient of expansion, so that it will not break when submitted to rapid heating.

Another purpose is to make a high silica grog that will have substantially no shrinkage upon subsequent firing up to the point where the excess silica in the grog crystallizes.

Another purpose is to make a refractory grog consisting of silica and kaolin and/ or ball clay with a minimum of fluxes.

Another purpose is to make a high silica grog capable of being heated rapidly and whose silica will be converted to cristobalite in service firing, without rupturing the re-' fractory in which the grog is used.

Another purpose is to make a refractory which, when it dissolves in the glass, will produce a minimum of strings, cords and stones, yet have a minimum porosity so it will be but slowly dissolved by the glass.

Another purpose is to make a minimum porosity refractory which, after firing in service, will contain a large amount of crystalline silica. I

Another purpose is to make a grog that requiresless water for casting, since it is near zero porosity.

The invention contemplates the use of this high silica grog to make refractory products that will be shipped unfired and be heated up when installed in the furnace. In the furnace, the excess silica will crystallize out as cristobalite and thereafter the products will not become cooled down to the alpha-beta cristobalite transformation range.

The invention also contemplates the use of this grog in making products that are fired, but which are fired to a temperature so low that the silica in the glassy grog will not crystallize out as cristobalite to an objectionable extent. The grog is defined as the fired or non-plastic portion of the body which has been ground so that the particle size is larger than 100-150 mesh. Thematrix is defined as the plastic or bonding clay and/or organic bond, plus finely divided grog material that is minus ice FIG. 5 is a curve showing the flux body with siliceousv grog fired to 800 C.

FIG. 6 shows two curves showing a flux body siliceous grog fired to 800 C.

FIG. 7 is a curve showing the characteristic expansion of cristobalite.

Many fire clays contain a considerable amount of free with silica distributed through the clay. The silica is usually quartz. Grosalmerode clay contains about 50% free silica. A well known clay, Kaosil, contains about 50%.

free silica of a slightly larger particle size than Grosalmerode clay. When clays containing free silica are calcined to make grog, the clay portion shrinks while the free silica expands, resulting in a high porosity; If fired high in an attempt to reduce the porosity, the silica transforms to one of the less dense forms of silica, usually cristobalite, the amount of cristobalite formed depending upon the temperature to which the mass is fired, the time of firing, and the size of the. silica particles. There is f' rapid expansion in firing Grosalmerode clay, owing to' the quartz transformation to cristobalite.

Clay tank blocks and glass melting 'pots' formerly were made of 5080% calcined Grosalmerode clay as grog and bonded by Grosalmerode clay andother bonding clays. 1 For this purpose the calcined Grosahnerode clay was fired to a temperature about cone 9 where there was little silica transformed to cristobalite. Such grog was porous and bodies made with it could not be burned to high term I peratures without further shrinkage. If bodies made with this grog were fired to a high temperature the cristobalite that was formed in the grog prevented the body being cooled or reheated without cracking.

instead .of the German clay. Attempts have been made to synthesize German clay, using silica and pure ball clays and kaolins. but whenever any composition containing an appreciable amount of free silica is fired high 1 enough tobe dense and to insure little further shrinkage,

the free silica be'comescristobalite and the characteristic rapid contraction at the cristobalite inversion range causes breaking of the product in cooling and cracking when it is reheated through the cristobalite inversion range.

I achieve these objects by mixing thoroughly pure silica with a pure kaolin or kaoliuitic clay, and/or ball -have reacted with silica to form mullite.

ing silica together with the small amount of impurities Rapid chilling holds the grog as a glassy mass and keeps the free "silica For this purpose -150 mesh. Some suitable organic bonds are goulac,

clay, firing them to a temperature approximately 3200" F. where the mixture is a glassy mass, quenching the mass from this high temperature and grinding it to make a grog. I use kaolins and ball clays with low total fluxes so as to keep the mixture as refractory as possible, for example Tako kaolin and #S'Frazier ball clay. In firing the mass to so high a temperature that it is a glassy mass and substantially non-porous, the alumina in the clay will in the clay and sand will be a glass.

from crystallizing out as cristobalite.

in preparing the grogthe silica should substantially.

A 2,990,289 Patented June 27, 1961 It is desirable to have a tank block or pot that shows 1 minimum shrinkage'in service. As a consequence, domes- .tic clays lower in silica became commonly to be used.

The remain-l rlp r l all through a 100 mesh screen, but for the purpose oi Mixfllre A intimate mixing, finer silica, say 80% through a 325 i V mesh, or finer still, will make a more uniform glassy grog g' Ten n clay By wt' ig l may be accomplished at a lower temperatl reor in: Georgia k li n 3 q qq t l e an m ar available for 5 Sfli 100 mesh 13 if? 9pqmt qni y b oarser than 0 s calc'in-ed k 1i 1 0 6 n 14 e temperature required depends pon the silica-aim w an m y be Q t n d from iliquidus ur Fused (slllca and kaolln) 100 mesh 3.3 from the silica alu'mina phase diagram'showrl as FIG Toial t x 7. 53 3 i7 i 2s erPha ia mr Ceramists, published 10 (silica in -gag; bz American Ceramic Society. The liquidus curve was Grog. otained from chemically pure constituents; namely, silica and alumina. Where a small amount of fluxes oc- Fused (slhca and kaolin) 10+100 mesh-H our inthe material the temperature may be somewhat j i r lov'ver than the liquidus curve illustrated in the diagram. 15 gfiifif 80 3%) jI he-curyes of FIGS, 1, 2,; 3 and 4: show that grogs ha vmg a large percentage of silica, when'fired to a sufii- 7 Mixture B c eitly. higtlll temperature for a sufficient length of time" an quenc ed, there no cristobalite formed, and a sub-- I tan ially straight linecurve results Usually grog that g g if ig g gf '5" 8 Contains 60% SiO must he fired longer or at a higher l kaolin 7 y u tsigferature than one containing alarger percentage of Fused (silica and ka01in) 100 mesh p It' isnecessary to chill or quench this mass rapidly to revent the silica crystallizing out as cristobalite on cool 25 gifi i g jjf ggggg 50 mg, This may be done by plunging it in water'if the Greg-L 7' masses are large or by cooling it rapidly in air if the i masses are smal or by any the method that will chill Fused (811m and H400 50 the massra'pidly. For example, Irria'keag'rog haying V I l 7 1 silicaw iiem of a'tSout 75 t% by mixing 55% Taro so 'fg i f j b 5L7) kaolin with'45% l ne silica 86-90% through 325, mesh g screen); fir tliis' mixture to approximately 3200 F. until Mimm C if has become aglas sy n ia ss and quench th riias s by. Matrix mapping-it into Water; Sn'l all pices about /2" di-ani e 1 t te may be chilled rapidly in airbut masses e2 appr'tixi as gfi f 32 day "7 3 matlyz "diameter shouldbe ater cooled, to pre: i 5 vent formation of etistelsaliie inthe seiner" of the mags. i 9 i mg 5 15 T Wheretheifiredgr' materials are in the'folzm of par- C ft- 15 ticlesabout /2 diame er or" larger, they w ll becrilslied cme gggaligt; :15 to fines before mu ing them with the bond- 40 Totalmatrix 50 ri-make gi'ogs'having a total silica coiite'nt of 60% m 6&0? (811m m'mamx 685%) -8l5% depending on the product in which'thegr'og'is' to I he'llsed. In each case I Want the rogsuliealittallyzero Fused (811m and mesh-m peio'sity and chilled after the high firing. The rapid 1 a1 a I i 6 or quenching isespecially ne'c'es'sai'yinthe grogs 5. 5 75 witHa high silica content; In a g'rog'withsilica' aslow o gmg as 60%, the amoun't of cristohalite formed is small so Mixture D the' t'end'ency to break wheiireheat'ed through thecristov i l balifeinversion'ralig'e not so great. The more silica v 1 i 8 iri'tlie grog, the greater necessity to chill it rapidly to Frazlgr #5 Tenn i c ay "7"? 10 the formation" of any cristoliali-te" in cooling.

The time and the'temperaturerequired to obtaina' G q -Q "r",- "7'11 "T""" lassymagsandthe' rapidity or quenching may'be de'- t trhiine'd' ljy'taking samples and makinga'n expansion e v e V cui' feito knew whether-the silica hasgli eiindisspiveg; F? B? 41 aiiafdinya' glassy m'asscontailfing mulliieiind la 's 'ie- Grog (5111 m 53%) If dcsimbleitdhavle grbghwith asyldfi y Fused (811103. andls30l1n);20+100 mesh as possible sbfasto make an ultimate productwitll'ia' low I porosity; Also a dense grog will not take up water q g which means lower water required for castin hence 3 mgrog 7.55% lower'drying shrinkage and faster drying. I'have' found I that if I fire a high silica composition to so high a tem-' perature that the mass is largely glass and mullite and a p quench this rapidly, a dense grog isformed that can then; C q rg gkg m f, f V 22' be heated up through the cristobalite inversion range M$ PP{b j9 Y f -i-- --'-'-V- fih ut ki I 7 Fus'edr(sil1ca and kaolln)100 mesh 19 These grogs are used n making various refractory x l products; among them tank blocks, glass melting pots, gf m m? i dEbltllS drawbars, floaters and other high silicafpro'd (Silica in matrix 51.8%) 7 ucts. The grog is groun t P l l i l' y Gmgip H l. i t 1 controlled, and mixed with plastic clays to form these Fused (sll ra' andkao1ln) -8+l00 mesh 51 pr' id -I r r '7 v t '7 is 1,, r r

i efollowing are illiistrativeef vaijiblls'jslilifalil e cdfrl I 'I fotalgrog -5'1" positions andmixtures" which 1 have em'ployed a V(Silicaingrog*75;5%-) r Mixture F Matrix: By wt. percent Frazier #5 Tenn. ball clay 8 S.G.P. Tenn. #1 clay 10 Georgia kaolin 7 Calcined kyanite-lOO mesh 20 Total matrix 45 (Silica in matrix 46.4%)

Grog:

Fused (silica and kaolin) 10+l00 mesh 55 Total grog 55 (Silica in grog 75.5%)

Mixture G Matrix:

Frazier #5 Tenn. ball clay 6 S.G.P. Tenn. #1 9 Georgia kaolin 5 Silica-100 mesh 5 Fused (silica and kaolin)l mesh 25 Total matrix 50 (Silica in matrix 65%) Grog:

Fused (silica and kao1in)10+ 100 mesh 50 Total grog 50 (Silica in grog 65%) When bodies formed of these mixtures were fired to 800 C., their linear expansion ranged from slightly more than 0.175%, for mixture F, to slightly more than 0.275% for mixture A.

Some of these products are shipped unfired, in which case the product is heated up in the furnace, or before being placed in the furnace and then it is not allowed tocool down to the cristobalite inversion range during the furnace operation for the lifetime of the piece. During the operation of the furnace the glass in the grog gradually transforms to cristobalite. cristobalite above its alphabeta transformation temperature has a gradual expansion curve, so that a product high in cristobalite is not subject to large expansion or contraction stresses unless its temperature is lowered to around 200300 C.

The curve of FIG. is shown as representative of a body with a substantially uniform expansion curve up to 800 C. This results from the use of a grog with approximately uniform expansion.

In FIG. 6, curve A shows the body when fired at such a temperature and such a time that no cristobalite has formed. Curve B shows the same body fired to such a temperature and for such a time that a portion of the free silica has crystalized as cristobalite with its characteristic rapid expansion at 200 to 300 C., which gives the desired result.

While the completed bodies can be shipped in an unfired condition, they can be previously fired to not higher than cone 8, to give them greater strength during shipment. The free silica would not crystalize at cone 8 for a short period.

For a curve showing cristobalite expansion characteristics, see A Study of Silica Refractories by J. Spotts McDowell, Transactions American Institute of Mining Engineers, 1917, page 2007, such a curve being shown in FIG. 7 of the drawing.

Grog prepared in the manner above described can be sold as a commercial product in itself, in which case the customer will mix it with bonding clay to form the shapes which he may desire.

I claim as my invention:

l. The steps in a method of forming refractories, which com-prise making a mixture that contains not substantially less than 60% silica and the remainder consisting of an alumina-containing material that is of the group which consists of kaolin and ball clay, firing the mixture to a point at which the alumina-containing material has reacted with the silica, to form mullite and glass, cooling the fired mixture with sufficient rapidity to prevent the formation of cristobalite to a substantial extent, grinding the fired mixture to form grog of desired sizes, of from .15 to fines, and thereafter mixing the grog with a bonding clay to form a refractory body, preliminary to final firing, the grog constituting not substantially less than 50% of the body, and the bonding clay not substantially more than 50% of the body.

2. The steps in a method of forming refractories, which comprise making a mixture that contains 60% to silica and the remainder consisting of an alumina-containing material that is of the group which consists of kaolin and ball clay, firing the mixture to a point at which the alumina-containing material has reacted with the silica, to form mullite and glass, cooling the fired mixture with sufficient rapidity to prevent the formation of cristobalite to a substantial extent, grinding the fired mixture to form grog of desired sizes of from .15" to fines, and thereafter mixing the grog with a bonding clay to form a refractory body, preliminary to final firing, the grog constituting not substantially less than 50% of the body, and the bonding clay not more than 50% of the body.

3. The steps in a method of forming refractories, which comprise making a mixture that contains not substantially less than 60% silica and the remainder consisting of an alumina-containing material that is of the group which consists of kaolin and ball clay, firing the mixture to a point at which the alumina-containing material has reacted with the silica, to form mullite and glass, cooling the fired mixture with sufiicient rapidity to prevent the formation of cristobalite to a substantial extent, grinding the fired mixture to grog sizes of from .15 to fines, and thereafter mixing the grog with a bonding clay to form a refractory body preliminary to final firing, the grog constituting not substantially less than 50% of the body, and the remainder the bonding clay that contains from 46% to 71% silica.

References Cited in the file of this patent UNITED STATES PATENTS 1,882,701 Alley Oct. 18, 1932 2,272,618 Fessler et al. Feb. 1-0, 1942 2,362,825 Hutchins Nov. 14, 1944 2,641,044 Bearer June 9, 1953 2,695,849 McMullen Nov. 30, 1954 

1. THE STEPS IN A METHOD OF FORMING REFRACTORIES, WHICH COMPRISE MAKING A MIXTURE THAT CONTAINS NOT SUBSTANTIALLY LESS THAN 60% SILICA AND THE REMAINDER CONSISTING OF AN ALUMINA-CONTAINING MATERIAL THAT IS OF THE GROUP WHICH CONSISTS OF KAOLIN AND BALL CLAY, FIRING THE MIXTURE TO A POINT AT WHICH THE ALUMINA-CONTAINING MATERIAL HAS REACTED WITH THE SILICA, TO FORM MULLITE AND GLASS, COOLING THE FIRED MIXTURE WITH SUFFICIENT RAPIDITY TO PREVENT THE FORMATION OF CRISTOBALITE TO A SUBSTANTIAL EXTENT, GRINDING THE FIRED MIXTURE TO FORM GROG OF DESIRED SIZES, OF FROM .15" TO FINES, AND THEREAFTER MIXING THE GROG WITH A BONDING CLAY TO FORM A REFRACTORY BODY, PRELIMINARY TO FINAL FIRING, THE GROG CONSTITUING NOT SUBSTANTIALLY LESS THAN 50% OF THE BODY, AND THE BONDING CLAY NOT SUBSTANTIALLY MORE THAN 50% OF THE BODY. 